EP1869112A1 - Method for producing polystyrene foam particles with a high density - Google Patents
Method for producing polystyrene foam particles with a high densityInfo
- Publication number
- EP1869112A1 EP1869112A1 EP06725579A EP06725579A EP1869112A1 EP 1869112 A1 EP1869112 A1 EP 1869112A1 EP 06725579 A EP06725579 A EP 06725579A EP 06725579 A EP06725579 A EP 06725579A EP 1869112 A1 EP1869112 A1 EP 1869112A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- range
- polystyrene
- melt
- foam particles
- polystyrene foam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
- B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/10—Applying counter-pressure during expanding
- B29C44/105—Applying counter-pressure during expanding the counterpressure being exerted by a fluid
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3461—Making or treating expandable particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/125—Water, e.g. hydrated salts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/16—Making expandable particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/03—Extrusion of the foamable blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
Definitions
- the invention relates to a process for the production of polystyrene foam particles having a bulk density in the range of 40 to 400 g / l by extrusion of a carbon dioxide and / or water blowing agent containing polystyrene melt through a nozzle and underwater granulation, wherein the underwater granulation at a pressure in the range of 1 - 30 bar is performed.
- Polystyrene foams are usually made with the aid of organic blowing agents, for example with volatile hydrocarbons, in particular pentane.
- organic blowing agents for example with volatile hydrocarbons, in particular pentane.
- pentane emitted during production and processing of EPS must be recovered. This is expensive and expensive. It therefore makes sense to replace these organic substances with harmless propellants in the longer term.
- One way to do this is to use water as a blowing agent.
- WO 99/48955 and WO 99/48958 disclose processes for producing polystyrene foam particles from polystyrene beads which contain water as blowing agent.
- the processes described are relatively complex, since in each case in a first processing step slightly foamed granules must be produced, which can then be processed, after energy-intensive drying, to the actual, much lower densities.
- DE-A 198 190 58 describes weakly foamed, organic blowing agent-containing EPS particles having a coarse cell structure, which are prepared by extrusion of a propellant-containing polystyrene melt and underwater granulation in a water bath with a temperature between 50 and 9O 0 C and 2 to 20 bar pressure can be.
- WO 2004/022636 discloses a process which leads directly to foam particles of low density by extrusion of a blowing agent-containing polymer melt with water as blowing agent and a solubility promoter. This method is advantageous when the resulting foam particles are processed directly into foams, otherwise high transport costs are incurred due to the large volume.
- the object of the present invention was to find a simple process for the production of polystyrene foam particles having a bulk density in the range from 40 to 400 g / l, which works without organic blowing agents and has a homogeneous foam structure.
- the blowing agent used is water, CO 2 or mixtures thereof, preferably in amounts of 1 to 5% by weight, based on the polystyrene melt.
- solubility promoters such as alcohols, ketones, ethers or esters
- emulsifying aids such as amphiphilic organic compounds
- the blowing agent is mixed into the polymer melt.
- the process comprises the stages a) melt production, b) mixing c) cooling d) conveying and e) granulation.
- stages can be carried out by the apparatuses or apparatus combinations known in plastics processing.
- static or dynamic mixers are suitable, for example extruders.
- the polymer melt can be taken directly from a polymerization reactor or can be produced directly in the mixing extruder or a separate melt extruder by melting polymer granules.
- the cooling of the melt can be done in the mixing units or in separate coolers.
- the granulation takes place via the pressurized underwater granulation.
- Apparatus arrangements suitable for carrying out the method are, for example:
- the arrangement may include side extruders for incorporation of additives, e.g. of solids or thermally sensitive additives.
- the propellant-containing styrene polymer melt is usually supported at a temperature in the range of 140 to 300 0 C, preferably in the range of 160 to 24O 0 C through the nozzle plate. Cooling down to the range of the glass transition temperature is not necessary.
- the nozzle plate is heated at least to the temperature of the blowing agent-containing polystyrene melt.
- the temperature of the nozzle plate is in the range of 20 to 100 ° C above the temperature of the blowing agent-containing polystyrene melt. This prevents polymer deposits in the nozzles and ensures trouble-free granulation.
- the granulation is carried out according to the invention by underwater granulation at a pressure in the range of 1 to 30 bar, preferably in the range of 2 to 12 bar.
- the variable counter-pressure can be used to set the density and thus the bulk density of the polystyrene foam particles. While unfoamed, expandable Polystyrene particles have a bulk density of about 600-700 g / l, the pressure is selected according to the method of the invention so that slightly foamed polystyrene foam particles having a bulk density in the range of 40 to 400 g / l, preferably 50 to 300 g / l be obtained.
- the styrenic polymer melt may contain additives, nucleating agents, fillers, plasticizers, flame retardants, soluble and insoluble inorganic and / or organic dyes and pigments, e.g. IR absorbers such as carbon black, graphite or aluminum powder together or spatially separated, e.g. be added via mixer or side extruder.
- the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 5 wt .-%.
- a dispersing assistant for example organosilanes, polymers containing epoxy groups or maleic anhydride-grafted styrene polymers.
- Preferred plasticizers are mineral oils, low molecular weight styrene polymers, phthalates, which can be used in amounts of 0.05 to 10 wt .-%, based on the styrene polymer.
- the particle foam moldings according to the invention exhibit a high closed cell density, with more than 60%, preferably more than 70, more preferably more than 80% of the cells of the individual foam particles being closed-celled as a rule.
- Suitable fillers are organic and inorganic powders or fibrous materials, as well as mixtures thereof.
- organic fillers z As wood flour, starch, flax, hemp, ramie, jute, sisal-cotton cellulose or Aramidfasem be used.
- inorganic fillers z As silicates, barite, glass beads, zeolites or metal oxides are used.
- the mean particle diameter or, in the case of fibrous fillers, the length should be in the range of the cell size or smaller. Preference is given to an average particle diameter in the range from 1 to 100 ⁇ m, preferably in the range from 2 to 50 ⁇ m.
- the nature and amount of the fillers can influence the properties of the expandable thermoplastic polymers and the particle foam moldings obtainable therefrom.
- the proportion of the filler is generally in the range of 1 to 50, preferably 5 to 30 wt .-%, based on the thermoplastic polymer. At filler contents in the range of 5 to 15 wt .-%, no significant deterioration of the mechanical properties of the particle foams, such as flexural strength or Compressive strength observed.
- adhesion promoters such as maleic anhydride-modified styrene copolymers, epoxide group-containing polymers, organosilanes or styrene copolymers with isocyanate or acid groups, can markedly improve the binding of the filler to the polymer matrix and thus the mechanical properties of the particulate foam moldings.
- inorganic fillers reduce flammability.
- inorganic powders such as aluminum hydroxide
- Fillers with particle sizes in the range of 0.1 to 100 .mu.m, in particular in the range of 0.5 and 10 microns result in polystyrene foam at levels of 10 wt .-%, a reduction in thermal conductivity by 1 to 3 mW. Therefore, comparatively low thermal conductivities can be achieved even with smaller amounts of Ir absorbers, such as soot and graphite.
- an IR absorber such as carbon black or graphite, in amounts of from 0.1 to 10% by weight, in particular in amounts of from 2 to 8% by weight.
- carbon black when using smaller amounts of fillers, eg. B. under 5 wt .-%, it is also possible to use carbon black in amounts of 1 to 25 wt .-%, preferably in the range of 10 to 20 wt .-%. At these high carbon black contents, the carbon black addition is preferably mixed into the styrene polymer melt via the main stream and a side stream extruder.
- the addition via extruder allows a simple comminution of the carbon black agglomerates to an average agglomerate size in the range from 0.3 to 10 .mu.m, preferably in the range from 0.5 to 5 .mu.m, and homogeneous dyeing of the expandable styrene polymer granules, which can be foamed to form closed-cell foam particles.
- the particle foams obtainable with 10 to 20 wt .-% carbon black by foaming and sintering ⁇ achieve a thermal conductivity, measured at 10 0 C in accordance with DIN 52612, in the range of 30 to 33mW / mK.
- the BET surface area is preferably in the range of 10 to 120 m 2 / g.
- the graphite used is preferably graphite having an average particle size in the range from 1 to 50 ⁇ m.
- Hexabromocyclododecane can be used as flame retardant and dicumyl or dicumyl peroxide as flame retardant synergist.
- the weight ratio of Flame retardant synergist to organic bromine compound is generally in the range of 1 to 20, preferably in the range of 2 to 5.
- nucleating agents can be incorporated into the polymer melt.
- inorganic or organic fillers in amounts of up to 50% by weight, preferably up to 30% by weight, also have a supporting effect.
- the inventive method is characterized by the fact that it contains no volatile organic compounds due to the use of CO 2 or water as the blowing agent and the density and foam structure can be adjusted specifically.
- the polystyrene foam particles of the invention can be used for the production of foam moldings. They are preferably used in steam or a gas mixture containing at least 50 vol .-% water, foamed at temperatures of preferably 100 to 130 0 C at even lower bulk densities and subsequently welded to form foam moldings. To achieve particularly low bulk densities, for example less than 25 g / l, in particular between 8 and 16 g / l, foaming can be carried out several times in this manner, the granules being stored intermediately between the foaming steps and possibly dried.
- blowing agent-containing melt of originally 260 0 C to a temperature of 190 0 C
- a filler was optionally added together with polystyrene via a side stream extruder in the main stream and the resulting melt at 60 kg / h through a die plate with 32 holes (diameter nozzle 0.75 mm). promotes.
- pressurized underwater granulation 8 bar
- foamed granules with narrow size distribution were produced.
- the amounts of the blowing agents and fillers indicated in Table 1 relate to the melt in front of the nozzle plate.
- the foamed, dry particles were further foamed in a prefoamer for 2 minutes by means of steam of 12O 0 C to a bulk density of 30 g / l. Further reduction of the bulk density to 10 g / l was achieved by drying at 70 0 C and subsequent steaming with steam of 12O 0 C.
- Schaustoffform stresses were obtained by the prefoamed, dry foam particles were filled into a block mold with pressure and applied with steam of 120 ° C.
- the foam structures of the obtained foam molded articles were uniform with cell numbers in the range of 2 to 12 cells / mm with a standard deviation of less than 5.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a method for producing polystyrene foam particles with a bulk density ranging between 40 and 400 g/l by the extrusion of a polystyrene melt, containing carbon dioxide and/or water as the expansion agent, through a nozzle and by underwater granulation. According to the invention, the underwater granulation is carried out at a pressure ranging between 1 and 30 bar.
Description
Verfahren zur Herstellung von Polystyrolschaumpartikeln hoher DichteProcess for the production of polystyrene foam particles of high density
Beschreibungdescription
Die Erfindung betrifft ein Verfahren zur Herstellung von Polystyrol-Schaumpartikeln mit einem Schüttgewicht im Bereich von 40 bis 400 g/l durch Extrusion einer Kohlendioxid und/oder Wasser als Treibmittel enthaltenden Polystyrolschmelze durch eine Düse und Unterwassergranulierung, wobei die Unterwassergranulierung bei einem Druck im Bereich von 1 - 30 bar durchgeführt wird.The invention relates to a process for the production of polystyrene foam particles having a bulk density in the range of 40 to 400 g / l by extrusion of a carbon dioxide and / or water blowing agent containing polystyrene melt through a nozzle and underwater granulation, wherein the underwater granulation at a pressure in the range of 1 - 30 bar is performed.
Polystyrol-Schaumstoffe werden üblicherweise mit Hilfe organischer Treibmittel hergestellt, beispielsweise mit flüchtigen Kohlenwasserstoffen, insbesondere Pentan. Aus Umweltschutzgründen muss bei der Herstellung und Verarbeitung von EPS emittiertes Pentan wieder aufgefangen werden. Dies ist aufwendig und kostenintensiv. Es ist da- her sinnvoll, längerfristig diese organischen Substanzen durch unbedenkliche Treibmittel zu ersetzen. Ein Weg dazu ist die Verwendung von Wasser als Treibmittel.Polystyrene foams are usually made with the aid of organic blowing agents, for example with volatile hydrocarbons, in particular pentane. For environmental reasons, pentane emitted during production and processing of EPS must be recovered. This is expensive and expensive. It therefore makes sense to replace these organic substances with harmless propellants in the longer term. One way to do this is to use water as a blowing agent.
Aus WO 99/48955 und WO 99/48958 sind Verfahren zur Herstellung von Polystyol- Schaumstoffpartikeln aus Polystyrolperlen bekannt, welche Wasser als Treibmittel ent- halten. Die beschriebenen Verfahren sind jedoch relativ aufwändig, da jeweils in einem ersten Verarbeitungsschritt leicht angeschäumte Granulate hergestellt werden müssen, die dann, nach energieintensiver Trocknung, zu den eigentlichen, weitaus niedrigeren Dichten verarbeitet werden können.WO 99/48955 and WO 99/48958 disclose processes for producing polystyrene foam particles from polystyrene beads which contain water as blowing agent. However, the processes described are relatively complex, since in each case in a first processing step slightly foamed granules must be produced, which can then be processed, after energy-intensive drying, to the actual, much lower densities.
Die DE-A 198 190 58 beschreibt schwach angeschäumte, organische Treibmittel enthaltende EPS-Partikel mit grober Zellstruktur, die durch Extrusion einer treibmittelhalti- gen Polystyrolschmelze und Unterwassergranulierung in einem Wasserbad mit einer Temperatur zwischen 50 und 9O0C und 2 bis 20 bar Druck hergestellt werden können.DE-A 198 190 58 describes weakly foamed, organic blowing agent-containing EPS particles having a coarse cell structure, which are prepared by extrusion of a propellant-containing polystyrene melt and underwater granulation in a water bath with a temperature between 50 and 9O 0 C and 2 to 20 bar pressure can be.
Aus WO 2004/022636 ist ein Verfahren bekannt, das durch Extrusion einer treibmittel- haltigen Polymerschmelze mit Wasser als Treibmittel und einem Löslichkeitsvermittler direkt zu Schaumpartikeln niedriger Dichte führt. Dieses Verfahren ist dann vorteilhaft, wenn die erhaltenden Schaumpartikel direkt zu Schaumstoffen weiterverarbeitet werden, da andernfalls aufgrund des großen Volumens hohe Transportkosten anfallen.WO 2004/022636 discloses a process which leads directly to foam particles of low density by extrusion of a blowing agent-containing polymer melt with water as blowing agent and a solubility promoter. This method is advantageous when the resulting foam particles are processed directly into foams, otherwise high transport costs are incurred due to the large volume.
Aufgabe der vorliegenden Erfindung war es, ein einfaches Verfahren zur Herstellung von Polystyrol-Schaumpartikeln mit einem Schüttgewicht im Bereich von 40 bis 400 g/l zu finden, das ohne organische Treibmittel auskommt und eine homogene Schaumstruktur aufweist.The object of the present invention was to find a simple process for the production of polystyrene foam particles having a bulk density in the range from 40 to 400 g / l, which works without organic blowing agents and has a homogeneous foam structure.
Demgemäß wurde das eingangs beschriebene Verfahren gefunden.
Als Treibmittel wird Wasser, CO2 oder Mischungen davon bevorzugt in Mengen von 1 - 5 Gew.-%, bezogen auf die Polystyrolschmelze, eingesetzt. In der Regel werden der Polystyrolschmelze keine weiteren Treibmittel, Löslichkeitsvermittler, wie Alkohole, Ketone, Ether oder Ester oder Emulgierhilfsmittel, wie amphiphile organische Verbin- düngen zugesetzt.Accordingly, the method described above was found. The blowing agent used is water, CO 2 or mixtures thereof, preferably in amounts of 1 to 5% by weight, based on the polystyrene melt. As a rule, no further blowing agents, solubility promoters, such as alcohols, ketones, ethers or esters or emulsifying aids, such as amphiphilic organic compounds, are added to the polystyrene melt.
Zur Herstellung der erfindungsgemäßen Polystyrol-Schaumpartikel wird das Treibmittel in die Polymerschmelze eingemischt. Das Verfahren umfasst die Stufen a) Schmelzerzeugung, b) Mischen c) Kühlen d) Fördern und e) Granulieren. Jede dieser Stufen kann durch die in der Kunststoffverarbeitung bekannten Apparate oder Apparatekombinationen ausgeführt werden. Zur Einmischung eignen sich statische oder dynamische Mischer, beispielsweise Extruder. Die Polymerschmelze kann direkt aus einem Polymerisationsreaktor entnommen werden oder direkt in dem Mischextruder oder einem separaten Aufschmelzextruder durch Aufschmelzen von Polymergranulaten er- zeugt werden. Die Kühlung der Schmelze kann in den Mischaggregaten oder in separaten Kühlern erfolgen. Die Granulierung erfolgt über die druckbeaufschlagte Unterwas- sergranulierung. Zur Durchführung des Verfahrens geeignete Apparateanordnungen sind z.B.:To prepare the polystyrene foam particles according to the invention, the blowing agent is mixed into the polymer melt. The process comprises the stages a) melt production, b) mixing c) cooling d) conveying and e) granulation. Each of these stages can be carried out by the apparatuses or apparatus combinations known in plastics processing. For mixing, static or dynamic mixers are suitable, for example extruders. The polymer melt can be taken directly from a polymerization reactor or can be produced directly in the mixing extruder or a separate melt extruder by melting polymer granules. The cooling of the melt can be done in the mixing units or in separate coolers. The granulation takes place via the pressurized underwater granulation. Apparatus arrangements suitable for carrying out the method are, for example:
a) Polymerisationsreaktor - statischer Mischer/Kühler - Granulator b) Polymerisationsreaktor - Extruder - Granulator c) Extruder - statischer Mischer - Granulator d) Extruder - Granulatora) Polymerization Reactor - Static Mixer / Cooler Granulator b) Polymerization Reactor - Extruder - Granulator c) Extruder - Static Mixer - Granulator d) Extruder - Granulator
Weiterhin kann die Anordnung Seitenextruder zur Einbringung von Additiven, z.B. von Feststoffen oder thermisch empfindlichen Zusatzstoffen aufweisen.Furthermore, the arrangement may include side extruders for incorporation of additives, e.g. of solids or thermally sensitive additives.
Die treibmittelhaltige Styrolpolymerschmelze wird in der Regel mit einer Temperatur im Bereich von 140 bis 3000C, bevorzugt im Bereich von 160 bis 24O0C durch die Düsen- platte gefördert. Eine Abkühlung bis in den Bereich der Glasübergangstemperatur ist nicht notwendig.The propellant-containing styrene polymer melt is usually supported at a temperature in the range of 140 to 300 0 C, preferably in the range of 160 to 24O 0 C through the nozzle plate. Cooling down to the range of the glass transition temperature is not necessary.
Die Düsenplatte wird mindestens auf die Temperatur der treibmittelhaltigen Polystyrolschmelze beheizt. Bevorzugt liegt die Temperatur der Düsenplatte im Bereich von 20 bis 100°C über der Temperatur der treibmittelhaltigen Polystyrolschmelze. Dadurch werden Polymerablagerungen in den Düsen verhindert und eine störungsfreie Granulierung gewährleistet.The nozzle plate is heated at least to the temperature of the blowing agent-containing polystyrene melt. Preferably, the temperature of the nozzle plate is in the range of 20 to 100 ° C above the temperature of the blowing agent-containing polystyrene melt. This prevents polymer deposits in the nozzles and ensures trouble-free granulation.
Die Granulierung erfolgt erfindungsgemäß durch Unterwassergranulierung bei einem Druck im Bereich von 1 - 30 bar, bevorzugt im Bereich von 2 - 12 bar. Über den variablen Gegendruck kann die Dichte und damit das Schüttgewicht der Polystyrol- Schaumpartikel gezielt eingestellt werden. Während ungeschäumte, expandierbare
Polystyrolpartikel ein Schüttgewicht von etwa 600-700g/l aufweisen, wird nach dem erfindungsgemäßen Verfahren der Druck so gewählt, dass leicht angeschäumte PoI- sytrol-Schaumpartikel mit einem Schüttgewicht im Bereich von 40 bis 400 g/l, vorzugsweise auf 50 bis 300 g/l erhalten werden.The granulation is carried out according to the invention by underwater granulation at a pressure in the range of 1 to 30 bar, preferably in the range of 2 to 12 bar. The variable counter-pressure can be used to set the density and thus the bulk density of the polystyrene foam particles. While unfoamed, expandable Polystyrene particles have a bulk density of about 600-700 g / l, the pressure is selected according to the method of the invention so that slightly foamed polystyrene foam particles having a bulk density in the range of 40 to 400 g / l, preferably 50 to 300 g / l be obtained.
Des weiteren können der Styrolpolymerschmelze Additive, Keimbildner, Füllstoffe, Weichmacher, Flammschutzmittel, lösliche und unlösliche anorganische und/oder organische Farbstoffe und Pigmente, z.B. IR-Absorber, wie Ruß, Graphit oder Aluminiumpulver gemeinsam oder räumlich getrennt, z.B. über Mischer oder Seitenextruder zugegeben werden. In der Regel werden die Farbstoffe und Pigmente in Mengen im Bereich von 0,01 bis 30, bevorzugt im Bereich von 1 bis 5 Gew.-% zugesetzt. Zur homogenen und mikrodispersen Verteilung der Pigmente in dem Styrolpolymer kann es insbesondere bei polaren Pigmenten zweckmäßig sein ein Dispergierhilfsmittel, z.B Organosilane, epoxygruppenhaltige Polymere oder Maleinsäureanhydrid-gepfropfte Styrolpolymere, einzusetzen. Bevorzugte Weichmacher sind Mineralöle, niedermolekulare Styrolpolymere, Phthalate, die in Mengen von 0,05 bis 10 Gew.-%, bezogen auf das Styrolpolymerisat, eingesetzt werden können.Further, the styrenic polymer melt may contain additives, nucleating agents, fillers, plasticizers, flame retardants, soluble and insoluble inorganic and / or organic dyes and pigments, e.g. IR absorbers such as carbon black, graphite or aluminum powder together or spatially separated, e.g. be added via mixer or side extruder. In general, the dyes and pigments are added in amounts ranging from 0.01 to 30, preferably in the range of 1 to 5 wt .-%. For the homogeneous and microdispersed distribution of the pigments in the styrene polymer, it may be expedient in particular for polar pigments to use a dispersing assistant, for example organosilanes, polymers containing epoxy groups or maleic anhydride-grafted styrene polymers. Preferred plasticizers are mineral oils, low molecular weight styrene polymers, phthalates, which can be used in amounts of 0.05 to 10 wt .-%, based on the styrene polymer.
Überraschenderweise zeigen der erfindungsgemäßen Partikelschaumformteile auch bei der Anwesenheit von Füllstoffen eine hohe Geschlossenzelligkeit, wobei in der Regel mehr als 60 %, bevorzugt mehr als 70, besonders bevorzugt mehr als 80 % der Zellen der einzelnen Schaumpartikel geschlossenzellig sind.Surprisingly, even in the presence of fillers, the particle foam moldings according to the invention exhibit a high closed cell density, with more than 60%, preferably more than 70, more preferably more than 80% of the cells of the individual foam particles being closed-celled as a rule.
Als Füllstoffe kommen organische und anorganische Pulver oder Faserstoffe, sowie Mischungen davon in Betracht. Als organische Füllstoffe können z. B. Holzmehl, Stärke, Flachs-, Hanf-, Ramie-, Jute-, Sisal- Baumwoll- Cellulose oder Aramidfasem eingesetzt werden. Als anorganische Füllstoffe können z. B. Silikate, Schwerspat, Glaskugeln, Zeolithe oder Metalloxide eingesetzt werden. Bevorzugt werden pulverförmige anorganische Stoffe, wie Talk, Kreide, Kaoiin (AI2(Si2O5)(OH)4), Aluminiumhydroxid, Magnesiumhydroxid, Aluminiumnitrit, Aluminiumsilikat, Bariumsulfat, Calciumcarbonat, Calciumsulfat, Kieselsäure, Quarzmehl, Aerosil, Tonerde oder Wollastonit oder Kugeloder faserförmige, anorganische Stoffe, wie Glaskugeln, Glasfasern oder Kohlefasern. Die mittleren Teilchendurchmesser bzw. bei faserförmigen Füllstoffen die Länge sollte im Bereich der Zellgröße oder kleiner liegen. Bevorzugt wird ein mittlerer Teilchen- durchmesser im Bereich von 1 bis 100 μm, bevorzugt im Bereich von 2 bis 50 μm.Suitable fillers are organic and inorganic powders or fibrous materials, as well as mixtures thereof. As organic fillers z. As wood flour, starch, flax, hemp, ramie, jute, sisal-cotton cellulose or Aramidfasem be used. As inorganic fillers z. As silicates, barite, glass beads, zeolites or metal oxides are used. Preference is given to pulverulent inorganic substances such as talc, chalk, kaoiin (Al 2 (Si 2 O 5 ) (OH) 4 ), aluminum hydroxide, magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz powder, Aerosil, alumina or wollastonite or spherical or fibrous inorganic materials such as glass beads, glass fibers or carbon fibers. The mean particle diameter or, in the case of fibrous fillers, the length should be in the range of the cell size or smaller. Preference is given to an average particle diameter in the range from 1 to 100 μm, preferably in the range from 2 to 50 μm.
Durch die Art und Menge der Füllstoffe können die Eigenschaften der expandierbaren thermoplastischen Polymeren und der daraus erhältlichen Partikelschaumformteile beeinflussen. Der Anteil des Füllstoffes liegt in der Regel im Bereich von 1 bis 50, be- vorzugt 5 bis 30 Gew.-%, bezogen auf das thermoplastische Polymer. Bei Füllstoffgehalten im Bereich von 5 bis 15 Gew.-% wird keine wesentliche Verschlechterung der mechanischen Eigenschaften der Partikelschaumstoffe, wie Biegefestigkeit oder
Druckfestigkeit beobachtet. Durch die Verwendung von Haftvermittlern, wie Maleinsäu- reanhydrid-modifizierte Styrolcopolymere, epoxidgruppenhaltige Polymere, Organosi- lane oder Styrolcopolymere mit Isocyanat- oder Säuregruppen kann die Anbindung des Füllstoffes an die Polymermatrix und damit die mechanischen Eigenschaften der Parti- kelschaumformteile deutlich verbessert werden.The nature and amount of the fillers can influence the properties of the expandable thermoplastic polymers and the particle foam moldings obtainable therefrom. The proportion of the filler is generally in the range of 1 to 50, preferably 5 to 30 wt .-%, based on the thermoplastic polymer. At filler contents in the range of 5 to 15 wt .-%, no significant deterioration of the mechanical properties of the particle foams, such as flexural strength or Compressive strength observed. The use of adhesion promoters, such as maleic anhydride-modified styrene copolymers, epoxide group-containing polymers, organosilanes or styrene copolymers with isocyanate or acid groups, can markedly improve the binding of the filler to the polymer matrix and thus the mechanical properties of the particulate foam moldings.
In der Regel verringern anorganische Füllstoffe die Brennbarkeit. Insbesondere durch Zusatz von anorganischen Pulvern, wie Aluminiumhydroxid kann das Brandverhalten deutlich verbessert werden.In general, inorganic fillers reduce flammability. In particular, by the addition of inorganic powders, such as aluminum hydroxide, the fire behavior can be significantly improved.
Füllstoffe mit Partikelgrößen im Bereich von 0,1 bis 100 μm, insbesondere im Bereich von 0,5 und 10 μm ergeben im Polystyrol-Schaumstoff bei Gehalten von 10 Gew.-% eine Absenkung der Wärmeleitfähigkeit um 1 bis 3 mW. Daher lassen sich schon bei geringeren Mengen an Ir-Absorbem, wie Ruß und Graphit vergleichsweise niedrige Wärmeleitfähigkeiten erreichen.Fillers with particle sizes in the range of 0.1 to 100 .mu.m, in particular in the range of 0.5 and 10 microns result in polystyrene foam at levels of 10 wt .-%, a reduction in thermal conductivity by 1 to 3 mW. Therefore, comparatively low thermal conductivities can be achieved even with smaller amounts of Ir absorbers, such as soot and graphite.
Bevorzugt wird zur Verringerung der Wärmeleitfähigkeit ein IR-Absorber, wie Ruß oder Graphit in Mengen von 0,1 bis 10 Gew.-%, insbesondere in Mengen von 2 bis 8 Gew.-% eingesetzt.To reduce the thermal conductivity, preference is given to using an IR absorber, such as carbon black or graphite, in amounts of from 0.1 to 10% by weight, in particular in amounts of from 2 to 8% by weight.
Bei Verwendung von geringeren Mengen an Füllstoffen, z. B. unter 5 Gew.-%, ist es auch möglich, Ruß in Mengen von 1 bis 25 Gew.-%, bevorzugt im Bereich von 10 bis 20 Gew.-% einzusetzen. Bei diesen hohen Rußgehalten wird die Rußzugabe bevorzugt aufgeteilt über den Hauptstrom- und einen Seitenstromextruder in die Styrolpoly- merschmelze eingemischt. Die Zugabe über Extruder ermöglicht eine einfache Zerkleinerung der Rußagglomerate auf eine mittlere Agglomeratgröße im Bereich von 0,3 bis 10 μm, bevorzugt im Bereich von 0,5 bis 5 μm und homogene Färbung der expandierbaren Styrolpolymergranulate, die zu geschlossenzelligen Schaumstoffpartikeln verschäumt werden können. Die mit 10 bis 20 Gew.-% Ruß nach Verschäumen und Versintern erhältlichen Partikelschaumstoffe erreichen eine Wärmeleitfähigkeit λ, bestimmt bei 100C nach DIN 52612, im Bereich von 30 bis 33 mW/mK.When using smaller amounts of fillers, eg. B. under 5 wt .-%, it is also possible to use carbon black in amounts of 1 to 25 wt .-%, preferably in the range of 10 to 20 wt .-%. At these high carbon black contents, the carbon black addition is preferably mixed into the styrene polymer melt via the main stream and a side stream extruder. The addition via extruder allows a simple comminution of the carbon black agglomerates to an average agglomerate size in the range from 0.3 to 10 .mu.m, preferably in the range from 0.5 to 5 .mu.m, and homogeneous dyeing of the expandable styrene polymer granules, which can be foamed to form closed-cell foam particles. The particle foams obtainable with 10 to 20 wt .-% carbon black by foaming and sintering λ achieve a thermal conductivity, measured at 10 0 C in accordance with DIN 52612, in the range of 30 to 33mW / mK.
Als Ruß wird bevorzugt Flammruß mit einer mittleren Teilchengröße im Bereich von 60 bis 150 nm, insbesondere im Bereich von 80 bis 120 nm eingesetzt. Die BET- Oberfläche liegt bevorzugt im Bereich von 10 bis 120 m2/g.Flame black having an average particle size in the range from 60 to 150 nm, in particular in the range from 80 to 120 nm, is preferably used as carbon black. The BET surface area is preferably in the range of 10 to 120 m 2 / g.
Als Graphit wird bevorzugt Graphit mit einer mittleren Teilchengröße im Bereich von 1 bis 50 μm eingesetzt.The graphite used is preferably graphite having an average particle size in the range from 1 to 50 μm.
Als Flammschutzmittel können Hexabromcyclododecan (HBCD) und als Flammschutzsynergist Dicumyl oder Dicumylperoxid eingesetzt werden. Das Gewichtsverhältnis von
Flammschutzsynergist zu organischer Bromverbindung liegt in der Regel im Bereich von 1 bis 20, bevorzugt im Bereich von 2 bis 5.Hexabromocyclododecane (HBCD) can be used as flame retardant and dicumyl or dicumyl peroxide as flame retardant synergist. The weight ratio of Flame retardant synergist to organic bromine compound is generally in the range of 1 to 20, preferably in the range of 2 to 5.
Zur besseren Kontrolle des Anschäumens können in die Polymerschmelze Nukleie- rungsmittel eingearbeitet werden. Unterstützend wirken hierbei auch anorganische oder organische Füllstoffe in Mengen bis zu 50 Gew.-%, bevorzugt bis zu 30 Gew.-%.For better control of intumescence, nucleating agents can be incorporated into the polymer melt. In this case, inorganic or organic fillers in amounts of up to 50% by weight, preferably up to 30% by weight, also have a supporting effect.
Zur Verbesserung der Expandierbarkeit und der Verträglichkeit der Füllstoffe mit der Polymermatix können weichmachende Additive oder Fließverbesserer, wie z.B. Weiß- öl, Pentan oder Joncryl ADF 1300 (Fa. Johnson Polymers, MW = 3.000 g/mol) in Mengen von 0,01 bis 20 Gew.-%, insbesondere 0,1 bis 5 Gew.-% dem Polystyrolgranulat zugegeben werden.To improve the expandability and compatibility of the fillers with the polymer matrix, plasticizing additives or flow improvers, such as e.g. White oil, pentane or Joncryl ADF 1300 (from Johnson Polymers, MW = 3,000 g / mol) in amounts of from 0.01 to 20% by weight, in particular from 0.1 to 5% by weight, are added to the polystyrene granules.
Das erfindungsgemäße Verfahren zeichnet sich dadurch aus, dass es aufgrund der Verwendung von CO2 oder Wasser als Treibmittel keine leichtflüchtigen organischen Verbindungen enthält und die Dichte und Schaumstruktur gezielt eingestellt werden kann.The inventive method is characterized by the fact that it contains no volatile organic compounds due to the use of CO 2 or water as the blowing agent and the density and foam structure can be adjusted specifically.
Die erfindungsgemäßen Polystyrol-Schaumpartikel können zur Herstellung von Schaumstoffformkörpern verwendet werden. Bevorzugt werden sie in Wasserdampf oder einem Gasgemisch, welches mindestens 50 Vol.-% Wasser enthält, bei Temperaturen um vorzugsweise 100 bis 1300C zu noch niedrigeren Schüttgewichten verschäumt und anschließend zu Schaumstoffformkörpern verschweißt. Zum Erzielen besonders niedriger Schüttdichten, beispielsweise weniger als 25 g/l, insbesondere zwischen 8 und 16 g/l kann mehrfach in dieser Weise geschäumt werden, wobei die Granulate zwischen den Schäumschritten zwischengelagert und unter Umständen getrocknet werden.The polystyrene foam particles of the invention can be used for the production of foam moldings. They are preferably used in steam or a gas mixture containing at least 50 vol .-% water, foamed at temperatures of preferably 100 to 130 0 C at even lower bulk densities and subsequently welded to form foam moldings. To achieve particularly low bulk densities, for example less than 25 g / l, in particular between 8 and 16 g / l, foaming can be carried out several times in this manner, the granules being stored intermediately between the foaming steps and possibly dried.
Beispiele:Examples:
Einsatzstoffe:Starting Materials:
Polystyrolschmelze aus Polystyrol PS 148G der BASF Aktiengesellschaft mit einerPolystyrene melt of polystyrene PS 148G from BASF Aktiengesellschaft with a
Viskositätszahl VZ von 83 ml/g, gewichtsmittleres Molekulargewicht Mw = 220.000 g/mol, Uneinheitlichkeit Mw/Mn = 2,8)Viscosity number VZ of 83 ml / g, weight-average molecular weight M w = 220,000 g / mol, non-uniformity Mw / Mn = 2.8)
Beispiele 1 - 4:Examples 1 - 4:
In eine Polystyrolschmelze wurde CO2 bzw. Wasser als Treibmittel eingemischt. Nach Abkühlen der treibmittelhaltigen Schmelze von ursprünglich 260 0C auf eine Tempera- tur von 190 0C wurde gegebenenfalls ein Füllstoff zusammen mit Polystyrol über einen Seitenstromextruder in den Hauptstrom zugegeben und die erhaltene Schmelze mit 60 kg/h durch eine Düsenplatte mit 32 Bohrungen (Durchmesser der Düse 0,75 mm) ge-
fördert. Mit Hilfe einer druckbeaufschlagten Unterwassergranulierung (8 bar) wurden angeschäumte Granulate mit enger Größenverteilung hergestellt. Die Mengen der in Tabelle 1 angegebenen Treibmittel und Füllstoffe beziehen sich auf die Schmelze vor der Düsenplatte.CO 2 or water as blowing agent was mixed into a polystyrene melt. After cooling the blowing agent-containing melt of originally 260 0 C to a temperature of 190 0 C, a filler was optionally added together with polystyrene via a side stream extruder in the main stream and the resulting melt at 60 kg / h through a die plate with 32 holes (diameter nozzle 0.75 mm). promotes. By means of pressurized underwater granulation (8 bar) foamed granules with narrow size distribution were produced. The amounts of the blowing agents and fillers indicated in Table 1 relate to the melt in front of the nozzle plate.
Die angeschäumten, trockenen Partikel wurden in einem Vorschäumer 2 Minuten lang mittels Wasserdampf von 12O0C auf eine Schüttdichte von 30 g/l weiter geschäumt. Weitere Reduktion der Schüttdichte auf 10 g/l wurde durch Trockenen bei 700C und anschließender Bedampfung mit Wasserdampf von 12O0C erreicht.The foamed, dry particles were further foamed in a prefoamer for 2 minutes by means of steam of 12O 0 C to a bulk density of 30 g / l. Further reduction of the bulk density to 10 g / l was achieved by drying at 70 0 C and subsequent steaming with steam of 12O 0 C.
Schaustoffformkörper wurden erhalten indem die vorgeschäumten, trockenen Schaumpartikel in eine Blockform mit Druck eingefüllt und mit Wasserdampf von 120°C beaufschlagt wurden.Schaustoffformkörper were obtained by the prefoamed, dry foam particles were filled into a block mold with pressure and applied with steam of 120 ° C.
Die Schaumstrukturen der erhaltenen Schaumstoffformkörper waren gleichmäßig mit Zellzahlen im Bereich von 2 bis 12 Zellen/mm mit einer Standardabweichung kleiner 5.The foam structures of the obtained foam molded articles were uniform with cell numbers in the range of 2 to 12 cells / mm with a standard deviation of less than 5.
Tabelle 1:Table 1:
Claims
1. Verfahren zur Herstellung von Polystyrol-Schaumpartikeln mit einem Schüttgewicht im Bereich von 40 bis 400 g/l durch Extrusion einer Kohlendioxid und/oder Wasser als Treibmittel enthaltenden Polystyrolschmelze durch eine Düse und Un- terwassergranulierung, dadurch gekennzeichnet, dass die Unterwassergranulie- rung bei einem Druck im Bereich von 1 - 30 bar durchgeführt wird.1. A process for the production of polystyrene foam particles having a bulk density in the range of 40 to 400 g / l by extrusion of a carbon dioxide and / or water as propellant-containing polystyrene melt through a nozzle and underwater granulation, characterized in that the underwater granulation at a pressure in the range of 1 - 30 bar is performed.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, dass als Treibmittel 1 - 5 Gew.-%, bezogen auf die Polystyrolschmelze, Kohlendioxid oder Wasser eingesetzt werden.2. The method according to claim 1, characterized in that as propellant 1-5 wt .-%, based on the polystyrene melt, carbon dioxide or water are used.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Unterwas- sergranulierung bei einem Druck im Bereich von 2 - 30 bar durchgeführt wird.3. The method according to claim 1 or 2, characterized in that the underwater sergranulierung is carried out at a pressure in the range of 2 - 30 bar.
4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Polystyrol-Schaumpartikel ein Schüttgewicht im Bereich von 50 bis 300 g/l aufweisen.4. The method according to any one of claims 1 to 3, characterized in that the polystyrene foam particles have a bulk density in the range of 50 to 300 g / l.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der Polystyrolschmelze 1 bis 50 Gew.-%, bezogen auf die Schmelze, eines Füllstoffes zugegeben werden.5. The method according to any one of claims 1 to 4, characterized in that the polystyrene melt 1 to 50 wt .-%, based on the melt, of a filler are added.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass als Füllstoff pulver- förmige anorganische Stoffe, wie Talk, Kreide, Kaolin, Aluminiumhydroxid,6. The method according to claim 4, characterized in that as a filler powdered inorganic substances such as talc, chalk, kaolin, aluminum hydroxide,
Magnesiumhydroxid, Aluminiumnitrit, Aluminiumsilikat, Bariumsulfat, Calciumcarbonat, Calciumsulfat, Kieselsäure, Quarzmehl, Aerosil,. Tonerde oder Wollastonit eingesetzt wird.Magnesium hydroxide, aluminum nitrite, aluminum silicate, barium sulfate, calcium carbonate, calcium sulfate, silica, quartz powder, aerosil ,. Alumina or wollastonite is used.
7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Polystyrolschmelze keine weiteren Treibmittel, Löslichkeitsvermittler oder Emul- gierhilfsmittel zugesetzt werden.7. The method according to any one of claims 1 to 6, characterized in that the polystyrene melt no further blowing agents, solubilizers or emulsifying aids are added.
8. Verwendung der nach einem Verfahren der Ansprüche 1 bis 7 hergestellten Po- lystyrol-Schaumpartikel zur Herstellung von Schaumstoffformkörpern. 8. Use of the polystyrene foam particles prepared by a process of claims 1 to 7 for the production of foam moldings.
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DE102005015891A DE102005015891A1 (en) | 2005-04-06 | 2005-04-06 | Process for the production of polystyrene foam particles of high density |
PCT/EP2006/061349 WO2006106120A1 (en) | 2005-04-06 | 2006-04-05 | Method for producing polystyrene foam particles with a high density |
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EP (1) | EP1869112A1 (en) |
KR (1) | KR20080005255A (en) |
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DE (1) | DE102005015891A1 (en) |
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US10358538B2 (en) * | 2009-10-27 | 2019-07-23 | Sekisui Plastics Co., Ltd. | Foamable polystyrene resin particles and polystyrene resin prefoamed particles |
US8889752B2 (en) * | 2010-06-11 | 2014-11-18 | Fina Technology, Inc. | Foamed articles exhibiting improved thermal properties |
US8770637B2 (en) * | 2010-07-08 | 2014-07-08 | Basf Se | Module for absorbing energy |
KR101419457B1 (en) * | 2012-08-24 | 2014-07-14 | 현대이피 주식회사 | method for manufacturing expandable styrene polymer containing aluminium particles, and expandable styrene polymer produced thereby |
CN105452355B (en) | 2013-06-13 | 2019-02-01 | 巴斯夫欧洲公司 | The preparation of expanded granular |
DE102015220203A1 (en) * | 2015-10-16 | 2017-04-20 | Alois Edler | Method and device for producing a polystyrene granulate |
KR20200125072A (en) | 2019-04-26 | 2020-11-04 | 한승훈 | Method and structure for constructing revetment |
CN114380616A (en) * | 2022-01-05 | 2022-04-22 | 江苏材睿科技有限公司 | Preparation method of foamed ceramic thermal insulation material and material obtained by preparation method |
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US4385016A (en) * | 1980-12-19 | 1983-05-24 | Phillips Petroleum Company | Method of extruding and pelletizing expandable polymeric composition with recycling of transparent water supplied across the face of the extrusion die |
US4636527A (en) * | 1985-04-12 | 1987-01-13 | The Dow Chemical Company | Method for the preparation of styrene polymer foam and foam prepared thereby |
EP0305862A1 (en) | 1987-09-04 | 1989-03-08 | General Electric Company | One-step process for the production of expandable foam beads |
DE19812854A1 (en) | 1998-03-24 | 1999-09-30 | Basf Ag | Foamed polystyrene particles |
DE19813108A1 (en) | 1998-03-25 | 1999-09-30 | Basf Ag | Process for the preparation of water-expandable styrene polymers |
DE19819058C5 (en) | 1998-04-29 | 2015-06-25 | Basf Se | Process for the production of prefoamed EPS particles with coarse foam structure from particulate, slightly foamed, expanded styrene polymers |
HUP0303866A3 (en) * | 2000-12-04 | 2008-03-28 | Nova Chem Inc | Foamed cellular particles of an expandable polymer composition |
DE10226749B4 (en) * | 2002-06-14 | 2014-09-04 | Basf Se | Process for producing expandable polystyrene |
DE10241298A1 (en) | 2002-09-04 | 2004-03-18 | Basf Ag | Process for the production of polystyrene foam particles with low bulk density |
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